CN104277498A

CN104277498A - Modified layered fillers and their use to produce nanocomposite compositions

Info

Publication number: CN104277498A
Application number: CN201410407374.5A
Authority: CN
Inventors: 龚才国; 翁卫青; 谢敏辅; A·J·迪亚斯; J·P·斯托克斯; A·A·加鲁斯卡; B·J·普尔; C·内亚古; K·卡普; M·W·约翰斯顿
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2004-12-03
Filing date: 2005-10-07
Publication date: 2015-01-14
Also published as: JP2008522000A; US20080081866A1; CA2588910C; US7825181B2; JP5255842B2; CN101111569A; CA2588910A1; WO2006062572A1; RU2007124695A; JP2011122159A; EP1836266A1; JP5560181B2; RU2391366C2; EP1836266B1

Abstract

The present invention relates to modified layered fillers made from layered fillers and modifying agents and processes to produce the same. The invention also relates to nanocomposite compositions made from these modified layered fillers and elastomers, and processes to produce the same, and their use in articles.

Description

The layered fillers of modification and they be used for preparing the purposes of nanocomposite composition

The application is the divisional application of Chinese patent application 200580047281.5.This application claims the rights and interests of the sequence number 60/632,828 submitted on December 3rd, 2004, the disclosure of the document is introduced for reference.

Invention field

The present invention relates to layered fillers of the modification of being made up of layered fillers and properties-correcting agent and preparation method thereof.The invention still further relates to the nanocomposite composition be made up of the layered fillers of these modifications and elastomerics, its preparation method and the purposes in goods thereof.

Background of invention

Nano composite material has been the theme of a lot of science and Industry literature, and this can give given material new performance owing to them largely.Specifically, polymer nanocomposites, as elastomerics-clay nanocomposites, has caused sizable interest.Nano composite material or polymer nanocomposites normally polymeric system as used herein, they comprise the inorganic particle of polymeric matrix, and this inorganic particle has at least one yardstick in nanometer range.

The preparation of nano composite material uses the method for many clays be peeling.A kind of the most frequently used method is to use organically-modified illiteracy unsticking soil.Organic clay via the preparation of solution class ion exchange reaction, usually knownly in this anti-applicable industry substitutes as organic molecule such as alkyl or aryl ammonium compound that is swelling or stripper the sodium ion be present on sodium montmorillonite surface usually.Such as, see, U.S. Patent number 5,807,629, WO 02/100935 and WO 02/100936.Other Background references comprises U.S. Patent number 5, and 576,373,5,665,183,5,807,629,5,936,023,6,121,361, WO 94/22680, WO 01/85831 and WO 04/058874.

But the long alkyl chains/type of many ammonium compounds limits separation (separation shown by d spacing such as between layer) and the consistency between alkyl chain and polymer backbone.Therefore, need the novel stripper of the layered fillers for improvement of modification, with the nanocomposite composition of the performance with improvement applied for the preparation of liner such as good barrier property.

Brief summary of the invention

In embodiments, the invention provides the layered fillers of the modification comprising at least one layered fillers and at least one properties-correcting agent, it is C that described properties-correcting agent comprises at least one carbon chain lengths ₂₅-C ₅₀₀polymer chain E and the functionalized group of ammonium.

In another embodiment, the invention provides nanocomposite composition, comprise: elastic composition, and comprise the layered fillers of modification of at least one layered fillers and at least one properties-correcting agent, it is C that described properties-correcting agent comprises at least one carbon chain lengths ₂₅-C ₅₀₀polymer chain E and the functionalized group of ammonium.

In still another embodiment, the invention provides the goods comprising nanocomposite composition, described composition comprises: elastic composition; Comprise the layered fillers of the modification of at least one layered fillers and at least one properties-correcting agent, it is C that described properties-correcting agent comprises at least one carbon chain lengths ₂₅-C ₅₀₀polymer chain E and the functionalized group of ammonium; At least one solidifying agent packaging (package); Optionally, the filler that at least one is additional, optionally, at least one linking agent, optionally, at least one processing aid, optionally, at least one plastomer; Or optionally, their mixture.

In any foregoing embodiments, the functionalized group of described ammonium can be described by the group be suspended to downside on polymer chain E:

Wherein each R, R ¹and R ²identical or different and independently selected from hydrogen, C ₁-C ₂₆alkyl, alkene or aryl, the C of replacement ₁-C ₂₆alkyl, alkene or aryl, C ₁-C ₂₆fatty alcohol or ether, C ₁-C ₂₆carboxylic acid, nitrile, ethoxylated amine, acrylate and ester; And wherein X is that the counterion of ammonium is as Br ^-, Cl ^-or PF ₆ ^-.

Accompanying drawing is sketched

Fig. 1 shows the d spacing plot figure of the clay of the modification of embodiment 1.

Fig. 2 shows the d spacing plot figure of the clay of the modification of embodiment 2.

Fig. 3 shows the d spacing plot figure of the clay of the modification of embodiment 3.

Fig. 4 shows the d spacing plot figure of the clay of the modification of embodiment 4.

Fig. 5 shows the d spacing plot figure of the clay of the modification of embodiment 8.

Fig. 6 shows the d spacing plot figure of the clay of the modification of embodiment 10.

Detailed Description Of The Invention

Now describing various specific embodiment of the present invention, variant and embodiment, comprising to understand the present invention in this preferred embodiment adopted and definition.In order to determine infringement, this scope of " invention " with reference to any one in claims or multinomial, comprise their equivalent and element or with those described restrictions be equal to.

When using at this, the new numbering plan of each race of the periodic table of elements according to CHEMICAL AND ENGINEERING NEWS, 63 (5), 27 (1985).

When using at this, polymkeric substance can be used to mean homopolymer, multipolymer, interpretation, terpolymer etc.Similarly, multipolymer can mean to comprise at least two kinds of monomers, optionally has the polymkeric substance of other monomer.

When using at this, when claiming polymkeric substance to comprise monomer, described monomer is present in polymkeric substance with the derivative form of the polymerized form of monomer or monomer.Similarly, when catalyst component is described as the neutral stable form comprising component, it will be understood by those skilled in the art that the ionic species for this component is to produce the form of polymkeric substance with monomer reaction.

When using at this, when the layered fillers of modification is described as comprising some component, those components with their synthesized form or derivative form (namely, the chemistry of accreditation such as between described component and Physical interaction, as those between layered fillers and properties-correcting agent interact) and/or the change that may occur between the synthesis phase of the laminated clay of modification exist.

When using at this, when nano composite material is described as comprising some component, those components with their synthesized form or derivative form (namely, the chemistry of accreditation such as between described component and Physical interaction, as those between the layered fillers and other component of elastomerics and modification interact) and/or the change that may occur between the synthesis phase of nano composite material exist.

When using at this, elastomerics used herein or elastic composition refer to the composition (blend of such as polymkeric substance) of any polymkeric substance or the polymkeric substance defined according to ASTM D 1566.Elastomerics comprises melt-mixing and/or the reactor blend of the blend such as polymkeric substance of the mixing of polymkeric substance.This term can use interchangeably with term " rubber ".

When using at this, " phr " is part/100 part rubber, and is conventional measuring in this area, and wherein the component of composition assigns to measure relative to main elastomer group, based on 100 weight parts of elastomer or rubber.

When using at this, Iso-butylene-based elastomers or polymkeric substance refer to and comprise at least 70mol% from the elastomerics of the repeating unit of iso-butylene or polymkeric substance.

When using at this, isoolefine refers to any olefinic monomer with at least one such carbon, and namely this carbon has two substituents thereon.

When using at this, polyene hydrocarbon refers to any monomer with two or more double bonds, and such as, polyene hydrocarbon can be that any monomer comprising two conjugated double bonds is if conjugated diolefine is as isoprene.

When using at this, nano composite material or nanocomposite composition refer to the polymeric system comprising inorganic particle in polymeric matrix, and described particle has at least one yardstick in nanometer range.

When using at this, insert the state referring to composition, wherein polymkeric substance is present between each layer of laminar filler.As in industry and academia approve, certain symbol of insertion can be the movements and/or weaken compared with original thin laminal filler of the lines that detect of X-ray, and this shows large than in primary mineral of space between vermiculite layers.

When using at this, peel off the separation referring to each layer of primary particle, so that polymkeric substance surrounds each particle.In one embodiment, very heteropolymer is present between each thin slice, so that thin slice can randomly be separated.Such as, certain index peeled off or insert can be the curve not showing X-ray lines or larger d spacing, because this random interval is the separation of the increase of laminar sheet, as discussed in more detail below.But as approved with academia in industry, other symbol may to illustrating that the result peeled off is useful, as testing permeability, submicroscopy, atomic force microscope etc.

When using at this, solvent refers to any material that can dissolve another kind of material.When using term " solvent ", unless otherwise prescribed, it can refer at least one solvent or two or more solvents.In certain embodiments, solvent is polarity; In other embodiments, solvent is nonpolar.

When using at this, solution refer to one or more materials (solute) in one or more materials (solvent) with molecular level or the homodisperse mixture of ion concentration.Such as, solution methods refers to that the layered fillers of elastomerics and modification all remains on the blending means in identical organic solvent or solvent mixture.

When using at this, hydrocarbon refers to and mainly comprises the molecule of hydrogen and carbon atom or the segment of molecule.In certain embodiments, hydrocarbon also comprises the halogenated form of hydrocarbon and comprises heteroatomic form, as discussed in more detail below.

Testing permeability carries out according to following explanation.Under Slow cooling by all embodiment compression molds to provide flawless pad.Compression and solidification press are used for rubber sample.The typical thickness of compression mold pad is approximately 0.38mm, and use Carver press, then punching out diameter from molding pad is 2 " disk be used for testing permeability.Before measuring, in the vacuum drying oven of 60 DEG C, these disks are nursed one's health a whole night.The principle using Mocon OX-TRAN 2/61 testing permeability device to describe in JOURNAL OF POLYMER SCIENCE the 8th volume: PART A-2467 (1970) according to people such as R.A.Pasternak at 40 DEG C carries out Oxygen permeation measurement.Prepared disk to be arranged in template and to seal with vacuum grease.The one side of this disk maintains the stable Oxygen Flow of 10mL/min, and on the another side of this disk, maintains the stable nitrogen gas stream of 10mL/min.Nitrogen side uses oxygen sensor, oxygen concn increase in time on nitrogen side can be monitored.Record oxygen penetrates the time required for this disk, or oxygen concn reaches the time required for steady state value on nitrogen side, and is used for determining Oxygen permeability.

X ray test carries out according to following explanation.Two different protractor configurations collect X-ray data.The D/MAX Rapid 2 with SAXS line block and pointolite is tieed up detector and is used for one group of data, and appendicular for the SAXS had in collimated beam pattern Ultima III line source is used for second group of data.Intensity shown in Fig. 1-6 to the curve of d spacing from the collimated beam pointolite with SAXS appurtenant instrument.For these data, by preparing sample to reduce the impact of preferred orientation relative to sample surfaces with different angles cutting various piece, and collimated beam is used to irradiate whole sample area.For the more information relevant with dependent program with carrying out these, please refer to the manufacture relevant to aforesaid device and operational manual.

Elastomerics

Other component that nano composite material of the present invention comprises at least one elastomerics and describes at this and require.In one embodiment, elastomerics can be interpretation.This interpretation can be C ₄-C ₇isomonoolefin (as iso-butylene) and p-alkylstyrene comonomer such as p-methylstyrene (preferably comprise at least 80wt%, more preferably at least 90wt% para-isomeride) random elastomeric copolymer, and optionally comprise functionalized interpolymer, at least one or more alkyl substituent be wherein present in styrenic monomer units comprises benzyl halide or some other functional groups.In another embodiment, interpretation is ethene or C ₃-C ₆alpha-olefin and p-alkylstyrene comonomer, preferably comprise the random elastomeric copolymer of at least 80wt% or at least p-methylstyrene of 90wt% para-isomeride, and optionally comprise functionalized interpolymer, at least one or more alkyl substituent be wherein present in styrenic monomer units comprises benzyl halide or some other functional groups.Exemplary material can be characterized by the interpretation comprising the following monomeric unit along the random interval of polymer chain:

Wherein R and R ¹be hydrogen independently, low alkyl group, as C ₁-C ₇alkyl and uncle or secondary alkylogen, X is that functional group is as halogen.In one embodiment, R and R ¹each hydrogen naturally.In one embodiment, the cinnamic 60mol% being at the most present in the para-orientation in interpretation structure can be functionalized structure (1) above, in another embodiment, is the 0.1-5mol% of total monomer units.In still another embodiment, the amount of functionalized structure (2) is the 0.4-2.5mol% of total monomer units.

Functional group X can be halogen or by other group as carboxylic acid; Carboxyl salt; Carboxyl ester, acid amides and imide; Hydroxyl; Alkoxide; Phenates; Thiolate; Thioether; Xanthogenate; Prussiate; Cyanate; Amino some other functional groups nucleophilic substitution of benzyl halide is introduced into their mixture.These functionalized isomonoolefin copolymers, its preparation method, functionizing method and curings, in the US patent No. 5,162, have carried out in 445 more specifically disclosing.

In one embodiment, described elastomerics comprises the interpretation of iso-butylene containing 0.5-20mol% p-methylstyrene and p-methylstyrene, wherein the methyl substituents be present in benzyl rings of 60mol% comprises bromine or chlorine atom at the most, as bromine atoms (to (bromometllylstyrene)), and the form of its acid or ester functional.

In another embodiment, when at high temperature mixed polymer component, functional group can with the functional group be present in matrix polymer through selecting to meet it, such as acid, amino or hydroxy functional group reaction or form polar link.

In certain embodiments, described interpretation has composition distribution uniformly substantially and makes at least 95wt% polymkeric substance have ring-alkylated styrenes structure division, and this has the average to alkylstyrene content of the polymkeric substance of 10% to ring-alkylated styrenes structure division.The feature of exemplary interpretation be to be less than 5 or be less than 2.5 narrow molecular weight distributions (Mw/Mn), and there is 25,000-750,000 by the exemplary number-average molecular weight of gel permeation chromatography.

Described elastomerics (interpretation as discussed above) can be prepared as follows: usually comprising halon as in the thinner of chlorinated hydrocarbon and/or fluorinated hydrocarbons (comprising their mixture), use lewis acid catalyst make monomer mixture slurry polymerization (see, such as WO 2004/058828, WO 2004/058827, WO 2004/058835, WO 2004/058836, WO 2004/058825, PCT/US03/41221 and WO 2004/058829), subsequently in the solution when there is halogen and radical initiator as in addition halogenation when heat and/or light and/or chemical initiator, preferred bromination, and optionally, subsequently with different functional moieties's electrophilic substitution bromines.

In one embodiment, poly-(isobutylene-co-p-methylstyrene) " BIMS " polymer phase of bromination comprises 0.1-5mol% bromometllylstyrene group usually for the total amount of the unit of monomer derived in this polymkeric substance.In another embodiment, the amount of Bromomethyl groups is 0.2-3.0mol%, be 0.3-2.8mol% in still another embodiment, be 0.4-2.5mol% in still another embodiment, be 0.3-2.0mol% in still another embodiment, wherein desirable scope can be any combination of any upper limit and any lower limit.According to another method for expressing, based on the weight of polymkeric substance, exemplary copolymers comprises 0.2-10wt% bromine, in another embodiment 0.4-6wt% bromine, 0.6-5.6wt% bromine in another embodiment, is substantially free of ring halogen or halogen in the polymer backbone.In one embodiment, interpretation is C ₄-C ₇the unit that the derivative unit (or isomonoolefin) of isoolefine, p-methylstyrene are derivative and the multipolymer to (halomethylstyrene) derivative unit, wherein the 0.4-3.0mol% based on p-methylstyrene sum to (halomethylstyrene) unit amount be present in interpretation, and the amount of unit that wherein p-methylstyrene derives is the 2wt%-25wt% (in one embodiment) based on total polymer, and 4wt%-15wt% (in another embodiment).In another embodiment, be to (bromometllylstyrene) to (halomethylstyrene).

In still another embodiment, described elastomerics can comprise halogenated butyl rubber component, it or be combined with described interpretation or as the clay of unique elastomerics with described stripping.In one embodiment of the invention, halogenated rubber component is C ₄-C ₆the halogenated copolymers of isoolefine and polyene hydrocarbon.In another embodiment, halogenated rubber component is polydiene or segmented copolymer, and C ₄-C ₆the blend of the multipolymer of isoolefine and conjugation or " star-branched " butyl polymer.Therefore halogenated butyl polymer useful in the present invention can be described as comprising C ₄-C ₇the unit that isoolefine is derivative, the unit that polyene hydrocarbon is derivative, and the halogenated elastomer of unit that halogenated multiolef iotan derives, and comprise " halogenated butyl rubber " and so-called " halogenated star-branched " isoprene-isobutylene rubber.

In one embodiment, halogenated butyl rubber is brominated butyl rubber, is chlorinated butyl rubber in another embodiment.(Robert F.Ohm edits at VANDERBILT RUBBER HANDBOOK 105-122 for the general property of halogenated butyl rubber and processing, R.T.Vanderbilt Co., Inc.1990) and in RUBBER TECHNOLOGY 311-321 (Maurice Morton edits, Chapman & Hall 1995) be described.Isoprene-isobutylene rubber, halogenated butyl rubber and star-branched butyl rubber by Edward Kresge and H.C.Wang at 8KlRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY 934-955 (John Wiley & Sons, Inc., the 4th edition .1993) in be described.

Halogenated rubber component of the present invention is including, but not limited to brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutene rubber, star-branched brominated butyl (polyisobutene/isoprene copolymer) rubber; Isobutylene bromomethylstyrene multipolymer is as iso-butylene/m-bromometllylstyrene, iso-butylene/p-bromometllylstyrene, iso-butylene/1-chloro-4-methyl-benzene, halogenated isobutylene cyclopentadiene, and iso-butylene/p-1-chloro-4-methyl-benzene, and as US 4,074,035 and US 4,395, the similar halomethylation aromatic interpolymers in 506; Isoprene and halogenated isobutylene multipolymer, sovprene, and analogue, and the mixture of any above-mentioned substance.Some embodiments of halogenated rubber component also at U.S. Patent number 4,703,09l and 4,632, be described in 963.

More particularly, in one embodiment, described elastomerics comprises halogenated butyl rubber.When using at this, " halogenated butyl rubber " not only refers to isoprene-isobutylene rubber but also refer to so-called " star-branched " isoprene-isobutylene rubber, as described below.Halogenated butyl rubber is made up of halogenating butyl rubber.Such as, the olefinic polyreaction charging for the preparation of halogenated butyl rubber of the present invention is those olefin(e) compounds being usually used in preparing butyl-type rubber polymer.Butyl polymer is made by making copolymerized monomer mixture react, and described mixture has at least (1) C ₄-C ₆isoolefin monomer component is as iso-butylene and (2) polyene hydrocarbon or conjugate diene monomer component.In one embodiment, isoolefine is the 70-99.5wt% of total comonomer mixture weight, is 85-99.5wt% in another embodiment.In one embodiment, the amount of conjugated diene component in copolymerized monomer mixture is 30-0.5wt%, is 15-0.5wt% in another embodiment.In still another embodiment, the 8-0.5wt% of copolymerized monomer mixture is conjugated diolefine.

Isoolefine is C ₄-C ₆compound is as iso-butylene, iso-butylene 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene and 4-methyl-1-pentene.Polyene hydrocarbon is C ₄-C ₁₄conjugated diolefine is as isoprene, divinyl, 2,3-dimethyl-1,3-butadiene, myrcene, 6,6-dimethyl-fulvene, cyclopentadiene, hexadiene and penta 2 rare.An embodiment of butyl rubber polymer of the present invention is by making 92-99.5wt% iso-butylene and 0.5-8wt% isoprene react, or makes 95-99.5wt% iso-butylene and 0.5-5.0wt% isoprene react in still another embodiment to obtain.

Halogenated butyl rubber is by making the halogenation of above-mentioned isoprene-isobutylene rubber product.Halogenation is undertaken by any mode, and the present invention does not limit by Halogenation process at this.Polymkeric substance if the halogenation method of butyl polymer is at U.S. Patent number 2,631,984,3,099,644,4,554,326,4,681,921,4,650,831,4,384,072,4,513,116 and 5,681, disclose in 901.In one embodiment, halogen in so-called II and III structure, such as, discussed in the 298-299 page (1995) of RUBBER TECHNOLOGY.In one embodiment, in hexane diluent, at 40-60 DEG C, bromine (Br is used ₂) or chlorine (C1 ₂) as halogenating agent by halogenating butyl rubber.In one embodiment, halogenated butyl rubber has 20-70, has the mooney viscosity of 25-55 (ML 1+8, at 125 DEG C) in another embodiment.Based on the weight of halogenated butyl rubber, halogen wt% is 0.1-10wt% in one embodiment, is 0.5-5wt% in another embodiment.In still another embodiment, the halogen wt% of halogenated butyl rubber is 1-2.2wt%.

In another embodiment, halobutyl or star-branched butyl rubber can make halogenation be in uncle's allylic positions through halogenation.This usually by the mode of free radical bromination or free radical chlorination and so on, or is realized by the method (as passed through heat rubber) of secondary treatment halogenated rubber and so on, to form allylic halogenated butyl and star-branched butyl rubber.Form the common method of allyl halide fluidized polymer at U.S. Patent number 4,632,963,4,649,178 and 4,703, disclose in 091.Therefore, in one embodiment of the invention, halogenated butyl rubber makes halogenated multiolefin units mainly allylic halogenated units, and wherein the amount of uncle's allylic configuration is at least 20mol% (total amount of relative halogenated multiolef iotan) in one embodiment, be at least 30mol% in another embodiment.This arrangement can be described as following (3), and wherein X is halogen, desirably chlorine or bromine, based on the total mole number of halogen, q is at least 60mol% in one embodiment, and being at least 30mol% in another embodiment, is 25-90mol% in still another embodiment:

The Commercial embodiments of halogenated butyl rubber of the present invention is Bromobutyl 2222 (ExxonMobil Chemical Company, Baytown, TX).For Bromobutyl 2222, its mooney viscosity is 27-37 (ML l+8, at 125 DEG C, ASTM 1646), and bromine content is 1.8-2.2wt%.In addition, the curing characteristics of Bromobutyl 2222 is as follows: MH is 28-40dNm, ML is 7-18dNm (ASTM D2084, modified version).Another Commercial embodiments of halogenated butyl rubber is Bromobutyl 2255 (ExxonMobil Chemical Company).Its mooney viscosity is 41-5l (ML 1+8, at 125 DEG C, ASTM 1646, modified version), and bromine content is 1.8-2.2wt%.In addition, the curing characteristics of Bromobutyl 2255 is as follows: MH is 34-48dNm, ML is 11-21dNm (ASTM D2084, modified version).The invention is not restricted to commercial source or the sign of above-mentioned any halogenated rubber component.

In another embodiment, described elastomerics can comprise branching or " star-branched " halogenated butyl rubber.In one embodiment, star-branched halogenated isoprene-isobutylene rubber (" SBHR ") is the isoprene-isobutylene rubber of halogenation or non-halogenation and the polydiene of halogenation or non-halogenation or the composition of segmented copolymer.Halogenation method at U.S. Patent number 4,074,035,5,071,913,5,286,804,5,182,333 and 6,228, describe in detail in 978.The present invention is not by the restriction of the method for formation SBHR.Polydiene/segmented copolymer or branching agent (hereinafter " polydiene ") normally cationoid reaction and exist in the polymerization process of butyl or halogenated butyl rubber, can with butyl or halogenated butyl rubber blended to form SBHR.Branching agent or polydiene can be any suitable branching agents, and the invention is not restricted to the type of the polydiene for preparing SBHR.

In one embodiment, the composition of the multipolymer of SBHR butyl normally as above or halogenated butyl rubber and following material: polydiene and the partially hydrogenated polydiene being selected from vinylbenzene, polyhutadiene, polyisoprene, poly-piperylene, natural rubber, styrene butadiene rubbers, ethylene-propylendiene rubber, styrene-butadiene-styrene and styrene isoprene styrene block copolymer (SIS).In certain embodiments, based on the amount of the monomer be present in polymkeric substance, the amount of polydiene is 0.3-3wt%, is greater than 0.3wt% in another embodiment, is 0.4-2.7wt% in still another embodiment.

A Commercial embodiments of SBHR of the present invention is Bromobutyl 6222 (ExxonMobil Chemical Company, Baytown, TX), it has mooney viscosity (the ML 1+8 of 27-37, at 125 DEG C, ASTM 1646, modified version), and the bromine content of 2.2-2.6wt% relative to SBHR.In addition, the curing characteristics of Bromobutyl 6222 is as follows: MH is 24-38dNm, ML is 6-16dNm (ASTM D2084, modified version).

In certain embodiments, halogenated rubber component amount is in the blend 10-90phr in one embodiment, 20-80phr in another embodiment, be 30-70phr in still another embodiment, wherein desirable scope can be any combination of any phr upper limit and any phr lower limit.

Above-mentioned polymkeric substance is commonly referred to isobutylene-based polymer.In certain embodiments, described elastomerics comprises isobutylene-based polymer.Some elastomericss below are also isobutylene-based polymer according to the definition provided at this.

In another embodiment, described elastomerics can also comprise " conventional rubber ".

In still another embodiment, described elastomerics can comprise natural rubber, polyisoprene rubber, poly-(styrene co-butadiene) rubber (SBR), polybutadiene rubber (BR), poly-(isoprene-co-butadiene) rubber (IBR), styrene isoprene butadiene rubber (SIBR) (SBBR), ethylene-propylene rubber (EPM), Ethylene-Propylene-Diene rubber (EPDM), polysulphide, paracril, propylene oxide polymer, star-branched butyl rubber and halogenated starbranched butyl rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutene rubber, star-branched brominated butyl (polyisobutene/isoprene copolymer) rubber, poly-(isobutylene-co-p-methylstyrene) and halogenation poly-(isobutylene-co-p-methylstyrene), the unit derived as iso-butylene, unit that p-methylstyrene derives and the terpolymer to the unit that bromometllylstyrene derives, and their mixture.

In another embodiment, described elastomerics can also comprise natural rubber.Natural rubber has been described in detail in RUBBER TECHNOLOGY 179-208 (Maurice Morton, Chapman & Hall 1995) by Subramaniam.The desirable embodiment of natural rubber of the present invention is selected from Malaysian rubber as SMR CV, SMR 5, SMR 10, SMR 20 and SMR 50 and their mixture, wherein said natural rubber has 30-120 at 100 DEG C, more preferably the mooney viscosity (ML 1+4) of 40-65.Carry out according to ASTM D-1646 at this Mooney viscosity test related to.

In another embodiment, described elastomerics can also comprise polyhutadiene (BR) rubber.The mooney viscosity (ML 1+4) that this polybutadiene rubber is measured at 100 DEG C can be 35-70, is 40-about 65 in another embodiment, is 45-60 in still another embodiment.These some commercial embodiments elastomeric useful in the present invention are NATSYN ^tM(Goodyear Chemical Company) and BUDENE ^tM1207 or BR 1207 (Goodyear Chemical Company).An example is high-cis polybutadiene (cis-BR).So-called " cis-polybutadiene " or " high-cis polybutadiene " refer to use Isosorbide-5-Nitrae-cis-polybutadiene, and wherein the amount of cis component is at least 95%.A particular instance of the high-cis polybutadiene commerical prod used in the composition is BUDENE ^tM1207.

In another embodiment, described elastomerics can also comprise the rubber of the unit of ethene and propylene derived as being also suitable as EPM and EPDM of additional rubber.The example manufacturing the comonomer be applicable in EPDM be ethylidene norbornene, Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene and other.These rubber are described in RUBBER TECHNOLOGY 260-283 (1995).The ethylene-propylene rubber be applicable to can be used as VISTALON ^tMbe purchased (ExxonMobil Chemical Company, Baytown, TX).

In another embodiment, described elastomerics can also comprise the part of halogenated rubber as terpolymer composition.

The general property of halogenated rubber and processing are such as, (Robert F.Ohm edits VANDERBILT RUBBER HANDBOOK 105-122, R.T.Vanderbilt Co., Inc.1990) and RUBBER TECHNOLOGY 311-321 (1995) in be described.Isoprene-isobutylene rubber, halogenated butyl rubber and star-branched butyl rubber by Edward Kresge and H.C.Wang at 8KlRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY 934-955 (John Wiley & Sons, Inc., 4th edition, 1993) be described in.

In certain embodiments, described elastomerics can also comprise one or more in following material: brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutene rubber, star-branched brominated butyl (polyisobutene/isoprene copolymer) rubber; Halogenation gathers (isobutylene-co-p-methylstyrene), the unit derived as iso-butylene, unit that p-methylstyrene derives and the terpolymer (BrIBMS) to the unit that bromometllylstyrene derives, with such as U.S. Patent number 5,162,445; 4,074,035; With 4,395, the similar halomethylation aromatic interpolymers in 506; Halogenated isoprene and halogenated isobutylene multipolymer, sovprene and analogue, and the mixture of any above-mentioned substance.Some embodiments of halogenated rubber component also at U.S. Patent number 4,703,09l and 4,632, be described in 963.

In another embodiment, described elastomerics can comprise so-called semi-crystalline co-polymers (" SCC ").Semi-crystalline co-polymers is described in WO 00/69966.Normally, in one embodiment, SCC is the unit of ethene or propylene derived and the multipolymer of alpha-olefin derived unit, described alpha-olefin is containing 4-16 carbon atom, in another embodiment, SCC is the unit of ethylene derivative and the multipolymer of alpha-olefin derived unit, and described alpha-olefin is containing 4-10 carbon atom, and wherein SCC has certain degree of crystallinity.In another embodiment, SCC is the multipolymer of the alpha-olefin derived unit of the unit that derives of 1-butylene and another kind, and described another kind of alhpa olefin is containing 5-16 carbon atom, and wherein SCC also has certain degree of crystallinity.SCC also can be ethene and cinnamic multipolymer.

The amount of described elastomerics in nano composite material can be 90phr at the most in one embodiment, can be 50phr at the most in another embodiment, can be 40phr at the most in another embodiment, can be 30phr at the most in still another embodiment.In still another embodiment, described elastomeric amount can be at least 2phr, can be at least 5phr in another embodiment, can be at least 5phr in still another embodiment, can be at least 10phr in still another embodiment.A desirable embodiment can comprise any combination of any phr upper limit and any phr lower limit.

Such as, the amount of described elastomerics (individually or as the blend of rubber as NR and BR) can be 5-90phr in one embodiment, can be 10-80phr in another embodiment, can be 30-70phr in still another embodiment, can be 40-60phr in still another embodiment, can be 5-50phr in still another embodiment, can be 5-40phr in still another embodiment, can be 20-60phr in still another embodiment, can be 20-50phr in still another embodiment, the embodiment selected depend on final utilization occasion needed for composition.

The polymeric constituent of nano composite material of the present invention can comprise the elastomerics described in any above-mentioned elastomerics of at least one maybe can to comprise in above-mentioned elastomerics at least two or more any combination.In one embodiment, described elastomerics comprises at least one isobutylene-based polymer.In another embodiment, described elastomerics comprises other rubber of at least one isobutylene-based polymer and at least one.In still another embodiment, described elastomerics comprises at least two or more isobutylene-based polymer.

The layered fillers of modification

Nano composite material can comprise the layered fillers of at least one elastomerics as above and at least one modification.The layered fillers of this modification can allow the method for at least one layered fillers as at least one laminated clay and at least one modifying agent prepare by comprising.

The method that the layered fillers of modification can be familiar with by those skilled in the art also uses them to be familiar with equipment to be prepared.Such as, see U.S. Patent number 4,569,923,5,663,111,6,036,765 and 6,787,592.The explanation of these methods provides in embodiment part.But this does not provide the intention of detailed bill.

In one embodiment, layered fillers such as laminated clay can comprise at least one silicate.

In certain embodiments, silicate can comprise at least one " montmorillonite " or " clay of smectite type ", and it refers to that a class has the clay mineral of the lattice of expansion.Such as, it can comprise the Dioctahedral smectite be made up of polynite, beidellite and nontronite, and trioctaedric smectite, and described trioctaedric smectite comprises saponite, hectorite and sauconite.Also comprise the montmorillonite-clay of synthesis preparation, such as, by U.S. Patent number 3,252,757,3,586,468,3,666,407,3,671,190,3,844,978,3,844,979,3,852,405 and 3,855, the synthesis of hydrothermal method disclosed in 147 preparation.

In other embodiment, at least one silicate can comprise natural or synthesis phyllosilicate, as polynite, nontronite, beidellite, wilkinite, volkonskoite, LAPONITE, hectorite, saponite, sauconite, magadiite, fibrous morphology crystals, rich magnesium montmorillonite etc., and vermiculite, halloysite, aluminate oxide, hydrotalcite etc.The combination of any foregoing embodiments also takes in.

Can be laminated clay modified as inserted or peeling off as described above by layered fillers: can experience and the properties-correcting agent of the cationic ion exchange reaction at the interlayer surface place being present in layered fillers or swelling agent or stripper process by least one.

It is C that the properties-correcting agent be applicable to can comprise at least one carbon chain lengths ₂₅-C ₅₀₀polymer chain, wherein this polymer chain also comprises the side described by following group and is suspended to ammonium functionalizing group on this polymer chain E:

At least one that can also comprise described properties-correcting agent can experience the additive reagent with the cationic ion exchange reaction at the interlayer surface place being present in layered fillers.Additional reagent comprises at least one cationic surfactant, as ammonium ion, and alkylamine or alkyl phosphate ion (primary, secondary, uncle and Ji), the phosphorus of aliphatic series, aromatics or arylaliphatic amines or sulfonium derivative, phosphine and sulfide etc.

In other embodiments, polymer chain can comprise C ₃₀-C ₄₀₀, preferred C ₃₀-C ₃₀₀, even more preferably C ₃₀-C ₂₀₀carbon chain lengths.

In another embodiment, polymer chain can comprise C ₄₀-C ₄₀₀, preferred C ₅₀-C ₃₀₀, even more preferably C ₆₀-C ₂₀₀carbon chain lengths.

In a preferred embodiment, polymer chain can comprise C ₂₅-C ₅₀₀carbon chain lengths, this carbochain is by C ₄-C ₇isoolefine such as iso-butylene is made.

In one embodiment, polymer chain comprises the derivative unit of the iso-butylene with ammonium functionalizing group as above.In another embodiment, polymer chain can be formed primarily of poly-(iso-butylene) with ammonium functionalizing group as above.In still another embodiment, properties-correcting agent can comprise the PIBA of at least one end-functionalization.

In other embodiment, polymer chain can comprise monomer, and described monomer comprises linearly, branching or cyclic alpha-olefin, as C ₃-C ₂₀alpha-olefin, C ₃-C ₁₀alpha-olefin, C ₃-C ₈alpha-olefin or C ₄-C ₆alpha-olefin.Example comprises and can be one or more in following material: butylene, amylene, hexene, heptene, octene, nonene, decene, dodecylene, 4-methyl pentene-1,3-methylpentene-1,3,5,5-trimethylhexene-1 and 5-ethyl-1-nonene.In an especially preferred embodiment, polymer chain comprises the iso-butylene with ammonium functionalizing group as above.

Polymer chain can also comprise monomer as the styrenic of styrenic and/or replacement and vinyl ether.Described styrenic can be replaced (on ring) by alkyl, aryl, halogenide or alkoxide groups.Preferably, described monomer comprises 2-20 carbon atom, more preferably 2-9, even more preferably 3-9 carbon atom.Example comprises vinylbenzene, to ring-alkylated styrenes, p-methylstyrene, alpha-methyl styrene, Vinylstyrene, di isopropenylbenzene, iso-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-amylene, isoprene, divinyl, 2,3-dimethyl-1,3-divinyl, beta-pinene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, penta 2 rare, methylvinylether, ethyl vinyl ether and an isobutyl vinyl ether etc.

In another embodiment, polymer chain can comprise one or more linear or branching C ₃-C ₃₀prochiral alpha-olefin or containing C ₅-C ₃₀the alkene of ring or its combination, can select catalyzer by Stereoselective and non-cubic and they be polymerized.When using at this, prochirality refers to the monomer being conducive to isotaxy or syndiotactic polymer formation when using stereospecific catalyst polymerization.

In other embodiments, polymer chain can comprise monomer, and this monomer comprises the monomer containing aromatic group containing 30 carbon atoms at the most.The monomer containing aromatic group be applicable to comprises at least one aromatic structure, preferred phenyl, indenyl, fluorenyl or naphthyl moieties.Monomer containing aromatic group also comprises at least one polymerisable double bond so that side is hung on polymer backbone by this aromatic structure after polymerisation.Monomer containing aromatic group can be replaced by one or more alkyl further, and described alkyl includes but not limited to C ₁-C ₁₀alkyl.In addition, two adjacent substituents can be connected to form ring texture.The preferred monomer containing aromatic group comprises at least one and is attached to aromatic structure on polymerizable olefinic structure division.Especially preferred aromatic monomer comprise vinylbenzene, alpha-methyl styrene, to ring-alkylated styrenes, Vinyl toluene, vinyl naphthalene, allyl benzene and indenes, especially vinylbenzene, p-methylstyrene, 4-phenyl-1-butylene and allyl benzene.

In another other embodiment, polymer chain can comprise monomer, and this monomer comprises the monomer containing non-aromatic cyclic groups.Such as, these monomers can contain 20 carbon atoms at the most.The monomer containing non-aromatic cyclic groups be applicable to preferably has at least one polymerizable ethylenic group, and this group is that the side in ring texture hangs group or belongs to a part for this ring texture.This ring texture can also further by one or more alkyl such as but be not limited to C ₁-C ₁₀alkyl replaces.The preferred monomer containing non-aromatic cyclic groups comprises vinyl cyclohexane, vinyl cyclohexene, vinyl norbornene, ethylidene norbornene, cyclopentadiene, cyclopentenes, tetrahydrobenzene, cyclobutene, vinyladamantane, norbornylene etc.

In another embodiment, polymer chain can comprise monomer, the diolefinic monomer that this monomer includes, and described diolefinic monomer comprises any hydrocarbon structure, such as, have the C of at least two unsaturated link(age)s ₄-C ₂₀hydrocarbon structure, wherein at least two unsaturated link(age)s can easily be selected in catalyzer introducing polymkeric substance by Stereoselective or non-cubic.Diolefinic monomer is selected from α, and ω-diene monomers (i.e. di-vinyl monomers) is preferred further.More preferably, diolefinic monomer is linear di-vinyl monomers, most preferably, containing those of 4-30 carbon atom.The example of preferred diene comprises divinyl, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, 11 carbon diene, 12 carbon diene, oleatridecadiene, 14 carbon diene, 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, 25 carbon diene; 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, especially preferred diene comprises 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-11 carbon diene, 1,11-12 carbon diene, 1,12-oleatridecadiene, 1,13-ten four carbon diene and low molecular weight polybutadiene (Mw is less than 1000g/mol).Preferred cyclic diene comprises cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, Vinylstyrene, dicyclopentadiene or having at each ring position or not having substituent diolefine containing more epipodium.

In still another embodiment, polymer chain can comprise unsaturated polar monomer, and described monomer comprises 6-nitro-1-hexene, N-methyl allyl amine, N-allyl cyclopentyl amine, N-allyl group-hexylamine, methyl vinyl ketone, ethyl vinyl ketone, 5-hexene-2-ketone, 2-ethanoyl-5-norbornylene, 7-cis methoxymethyl-5-norbornylene-2-ketone, propenal, 2,2-dimethyl-4-pentenals, undecylene aldehyde, 2,4-dimethyl-2,6-heptadienal, vinylformic acid, vinylacetic acid, 4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-pentadienoic acids, 2,6-heptadienoic acid, nine-fluoro-1-hexene, vinyl carbinol, 7-octene-1,2-glycol, 2-methyl-3-butene-1-alcohol, 5-norbornylene-2-nitrile, 5-norbornylene-2-formaldehyde, 5-norbornylene-2-carboxylic acid, cis-5-norbornylene-Nei-2,3-dicarboxylic acid, 5-norbornylene-2,2-dimethanol, cis-5-norbornylene-Nei-2,3-dicarboxylic anhydride, in the interior-3-of 5-norbornylene-2--dimethanol, outside the interior-3-of 5-norbornylene-2--dimethanol, 5-norbornylene-2-methyl alcohol, 5-norbornylene-2-alcohol, 5-norbornylene-2-yl acetate, 1-[2-(5-norbornylene-2-base) ethyl]-3,5,7,9,11,13,15-seven cyclopentyl five rings [9.5.1.1 ^3,9.l ^5,15.1 ^7,13] eight siloxanes, 2-benzoyl-5-norbornylene, allyl group 1, 1, 2, 2-tetrafluoro ether, acrolein dimethyl acetal, butadiene monoxide, 1, 2-epoxy group(ing)-7-octene, 1, 2-epoxy group(ing)-9-decene, 1,2-epoxy group(ing)-5-hexene, 2-methyl-2-vinyl oxirane, glycidyl allyl ether, DHF, 2-cyclopentene-1-one ethylidene acetal, allyl disulfide, ethyl propenoate and methyl acrylate.

In another other embodiment, polymer chain can comprise homopolymer or multipolymer.Preferred polymkeric substance comprises homopolymer or the multipolymer of any combination of one or more monomers as above.Especially preferred combination of monomers comprises 1) iso-butylene and p-methylstyrene; 2) iso-butylene and isoprene; With 3) homopolymer of iso-butylene.

Polymer chain can also comprise random or segmented copolymer.Preferred segmented copolymer comprises styrenic (such as vinylbenzene, p-methylstyrene, alpha-methyl styrene) and C ₄-C ₃₀the multipolymer of diolefine (such as isoprene, divinyl etc.).

In another preferred embodiment, polymer chain does not comprise the unit of propylene derived.

Foregoing embodiments any one in, ammonium functionalizing group as above comprises ammonium salt, and described ammonium salt comprises at least one , quaternary ammonium or tertiary amine salt.

Foregoing embodiments any one in, ammonium functionalizing group as above comprises the counterion of at least one ammonium salt, comprises Br ^-or Cl ^-.

In certain embodiments, the layered fillers of modification generally includes particle, and comprises and be present in tradable cat ions on interlayer surface as Na ⁺, Ca ^{+ 2}, K ⁺or Mg ^{+ 2}, described particle comprises the laminar sheet be closely linked that multiple thickness is 8-12 dust.

In one embodiment, such as, properties-correcting agent can be added in composition in any stage; Such as, can properties-correcting agent be added in elastomerics, then add layered fillers, or properties-correcting agent can be added in the binding substances of at least one elastomerics and at least one layered fillers; Or in still another embodiment, can first by properties-correcting agent and layered fillers blended, then add elastomerics.

In certain embodiments, such as properties-correcting agent described here is present in composition with the amount reaching best resistance to air loss (being measured by permeability test described here).Such as, can there is 0.1-40phr in described reagent in one embodiment, can there is 0.2-20phr in still another embodiment, can there is 0.3-10phr in another embodiment.

In certain embodiments, the spacing (as shown in by d spacing) of laminar sheet is improved.These are improved to desirable insertion or stripping is prepared, and when mixing with elastomerics to produce final nano composite material result, described insertion or stripping finally such as make goods such as liner application obtain the barrier property improved.

In certain embodiments, due to the reduction of ionic forces that laminar sheet is kept together with introduce molecule between laminar sheet (this is used for such as being greater than 4 dusts, or laminar sheet is separated by the distance being greater than 10 dusts), insertion or the stripping of the laminar sheet of layered fillers is caused as mentioned above with modifier treatment.

In other embodiments, the layered fillers of modification can comprise two or more d spacing is 30 dusts or larger layer; Or comprising two or more d spacing is 35 dusts or larger layer; Or comprising two or more d spacing is 40 dusts or larger layer; Or comprising two or more d spacing is 50 dusts or larger layer; Or comprising two or more d spacing is 75 dusts or larger layer; Or comprising two or more d spacing is 80 dusts or larger layer.

In certain embodiments, when by intercalating agent or stripper and base polymer material shear-mixed, during to provide the high degree of dispersion of the layered fillers of described modification in polymeric matrix, this separation makes the layered fillers of modification more easily absorb polymerisable monomer material and polymer materials between layers and promotes the leafing of laminar sheet further.

In certain embodiments, layered fillers and above-mentioned intercalating agent exchange in advance.Permutoid reaction is carried out and by mixing or heating assistance in solvent system.Then make the filler through exchanging and separated from solvent also dry to use in the preparation in nano composite material.The d spacing increased before and after exchanging and weight increase show the formation of modified clay.

Nano composite material is processed

Method and apparatus as known in the art can be used to prepare nano composite material, such as, include but not limited to melt-mixing and solution blending.Generally speaking, have nothing to do with adopted method, allow the layered fillers of at least one modification as above and at least one elastomer contact, in other embodiment, contact with elastomeric blend, to be prepared as follows shown nano composite material, such as, wherein symbol " Δ " represents heating.

Melt-mixing

The blended of component can be carried out as follows: at any applicable mixing equipment as Banbury ^tMmixing tank, Brabender ^tMin mixing tank or preferably mixing tank/forcing machine, the layered fillers knot of elastomerics and other optional component and modification is incorporated in such as 120 DEG C until carry out at the temperature of 300 DEG C mixing under being enough to make component disperses to the shearing condition of required homogeneity being formed nano composite material (see, such as U.S. Patent number 6,034,164,6,060,549, WO 02/48257 and WO 02/100923).

Solution blending

Nano composite material of the present invention also can be prepared by solution methods.In certain embodiments, the solution methods preparing nanocomposite composition on the spot can be comprised.In one embodiment, described method can be included in the solution comprising at least one solvent and allow at least one elastomerics and at least one layered fillers such as layered fillers as above contact.Can be used to prepare polymer nanocomposites of the present invention for the standard method of laboratory and scale operation and equipment (comprising interval and continuation method).

The solvent be applicable to comprises hydrocarbon as alkane, comprises C ₄-C ₂₂linearly, ring-type, branched alkane, alkene, aromatic substance and their mixture.Example comprises propane, Trimethylmethane, pentane, methylcyclopentane, isohexane, 2-methylpentane, 3-methylpentane, 2-methylbutane, 2, 2-dimethylbutane, 2, 3-dimethylbutane, 2-methyl hexane, 3-methyl hexane, 3-ethylpentane, 2, 2-dimethylpentane, 2, 3-dimethylpentane, 2, 4-dimethylpentane, 3, 3-dimethylpentane, 2-methylheptane, 3-ethyl hexane, 2, 5-dimethylhexane, 2, 2, 4-trimethylpentane, octane, heptane, butane, ethane, methane, nonane, decane, dodecane, undecane, hexane, methylcyclohexane, cyclopropane, tetramethylene, pentamethylene, methylcyclopentane, 1, 1-dimethylcyclopentane, cis 1, 2-dimethylcyclopentane, anti-form-1, 2-dimethylcyclopentane, anti-form-1, 3-dimethylcyclopentane, ethyl cyclopentane, hexanaphthene, methylcyclohexane, benzene, toluene, dimethylbenzene, o-Xylol, p-Xylol, m-xylene and their mixture.

In one embodiment, described solution comprises at least one hydrocarbon.In another embodiment, described solution is formed primarily of at least one hydrocarbon.In still another embodiment, described solution comprises or forms primarily of two or more hydrocarbon.In other embodiment, described solution can comprise at least one hexane, as the mixture of hexanaphthene or hexane.The commerical prod that the mixture of hydrocarbon can be used as low grade usually as the mixture of hexane obtains.

In another embodiment, the solvent be applicable to comprises one or more nitrated alkane, comprises C ₂-C ₂₂nitrated linear, ring-type or branched alkane.Nitrated alkane comprises, but be not limited to: Nitromethane 99Min., nitroethane, nitropropane, nitrobutane, nitropentane, nitrohexane, nitroheptane, nitrooctane, nitrodecane, nitrononane, nitrododecane, nitroundecane, nitrocycloethane, nitrocyclohexane, nitro cyclopropane, nitrocyclobutane, nitrocyclopentane, nitrocyclohexane, nitro suberane, nitrocyclodecane, nitrocyclononane, nitrocyclododecane, nitro cyclododecane, nitro ring undecane, oil of mirbane, with two and trinitro-form of above-mentioned substance, and their mixture.

Also the halogenated form of above-mentioned all substances can be used as chlorinated hydrocarbon, such as methyl chloride, methylene dichloride, monochloroethane, chloropropane, chlorobutane, chloroform and their mixture.

Also hydrofluoroalkane can be used, such as, methyl fuoride; Two methyl fuorides; Three methyl fuorides; Fluoroethane; 1,1-bis-fluoroethane; 1,2-bis-fluoroethane; 1,1,1-tri-fluoroethane; 1,1,2-tri-fluoroethane; 1,1,1,2-tetra flouroethane; 1,1,2,2-tetra flouroethane; 1,1,1,2,2-five fluoroethane; 1-fluoro-propane; 2-fluoro-propane; 1,1-bis-fluoro-propane; 1,2-bis-fluoro-propane; 1,3-bis-fluoro-propane; 2,2-bis-fluoro-propane; 1,1,1-tri-fluoro-propane; 1,1,2-tri-fluoro-propane; 1,1,3-tri-fluoro-propane; 1,2,2-tri-fluoro-propane; 1,2,3-tri-fluoro-propane; 1,1,1,2-tetra-fluoro-propane; 1,1,1,3-tetra-fluoro-propane; 1,1,2,2-tetra-fluoro-propane; 1,1,2,3-tetra-fluoro-propane; 1,1,3,3-tetra-fluoro-propane; 1,2,2,3-tetra-fluoro-propane; 1,1,1,2,2-five fluoro-propane; 1,1,1,2,3-five fluoro-propane; 1,1,1,3,3-five fluoro-propane; 1,1,2,2,3-five fluoro-propane; 1,1,2,3,3-five fluoro-propane; 1,1,1,2,2,3-hexafluoorpropane; 1,1,1,2,3,3-hexafluoorpropane; 1,1,1,3,3,3-hexafluoorpropane; 1,1,1,2,2,3,3-seven fluoro-propane; 1,1,1,2,3,3,3-seven fluoro-propane; Fluorobutane; 2-butyl fluoride; 1,1-bis-butyl fluoride; 1,2-bis-butyl fluoride; 1,3-bis-butyl fluoride; Isosorbide-5-Nitrae-two butyl fluoride; 2,2-bis-butyl fluoride; 2,3-bis-butyl fluoride; 1,1,1-tri-butyl fluoride; 1,1,2-tri-butyl fluoride; 1,1,3-tri-butyl fluoride; 1, Isosorbide-5-Nitrae-three butyl fluoride; 1,2,2-tri-butyl fluoride; 1,2,3-tri-butyl fluoride; 1,3,3-tri-butyl fluoride; 2,2,3-tri-butyl fluoride; 1,1,1,2-tetra-butyl fluoride; 1,1,1,3-tetra-butyl fluoride; 1,1, Isosorbide-5-Nitrae-four butyl fluoride; 1,1,2,2-tetra-butyl fluoride; 1,1,2,3-tetra-butyl fluoride; 1,1,2,4-tetra-butyl fluoride; 1,1,3,3-tetra-butyl fluoride; 1,1,3,4-tetra-butyl fluoride; 1, Isosorbide-5-Nitrae, 4-tetra-butyl fluoride; 1,2,2,3-tetra-butyl fluoride; 1,2,2,4-tetra-butyl fluoride; 1,2,3,3-tetra-butyl fluoride; 1,2,3,4-tetra-butyl fluoride; 2,2,3,3-tetra-butyl fluoride; 1,1,1,2,2-five butyl fluoride; 1,1,1,2,3-five butyl fluoride; 1,1,1,2,4-five butyl fluoride; 1,1,1,3,3-five butyl fluoride; 1,1,1,3,4-five butyl fluoride; 1,1, Isosorbide-5-Nitrae, 4-five butyl fluoride; 1,1,2,2,3-five butyl fluoride; 1,1,2,2,4-five butyl fluoride; 1,1,2,3,3-five butyl fluoride; 1,1,2,4,4-five butyl fluoride; 1,1,3,3,4-five butyl fluoride; 1,2,2,3,3-five butyl fluoride; 1,2,2,3,4-five butyl fluoride; 1,1,1,2,2,3-hexafluoro-butane; 1,1,1,2,2,4-hexafluoro-butane; 1,1,1,2,3,3-hexafluoro-butane; 1,1,1,2,3,4-hexafluoro-butane; 1,1,1,2,4,4-hexafluoro-butane; 1,1,1,3,3,4-hexafluoro-butane; 1,1,1,3,4,4-hexafluoro-butane; 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-butane; 1,1,2,2,3,3-hexafluoro-butane; 1,1,2,2,3,4-hexafluoro-butane; 1,1,2,2,4,4-hexafluoro-butane; 1,1,2,3,3,4-hexafluoro-butane; 1,1,2,3,4,4-hexafluoro-butane; 1,2,2,3,3,4-hexafluoro-butane; 1,1,1,2,2,3,3-seven butyl fluoride; 1,1,1,2,2,4,4-seven butyl fluoride; 1,1,1,2,2,3,4-seven butyl fluoride; 1,1,1,2,3,3,4-seven butyl fluoride; 1,1,1,2,3,4,4-seven butyl fluoride; 1,1,1,2,4,4,4-seven butyl fluoride; 1,1,1,3,3,4,4-seven butyl fluoride; 1,1,1,2,2,3,3,4-eight butyl fluoride; 1,1,1,2,2,3,4,4-eight butyl fluoride; 1,1,1,2,3,3,4,4-eight butyl fluoride; 1,1,1,2,2,4,4,4-eight butyl fluoride; 1,1,1,2,3,4,4,4-eight butyl fluoride; 1,1,1,2,2,3,3,4,4-nine butyl fluoride; 1,1,1,2,2,3,4,4,4-nine butyl fluoride; The fluoro-2-methylpropane of 1-; The fluoro-2-methylpropane of 1,1-bis-; The fluoro-2-methylpropane of 1,3-bis-; The fluoro-2-methylpropane of 1,1,1-tri-; The fluoro-2-methylpropane of 1,1,3-tri-; The fluoro-2-of 1,3-bis-(fluoromethyl) propane; The fluoro-2-methylpropane of 1,1,1,3-tetra-; The fluoro-2-methylpropane of 1,1,3,3-tetra-; The fluoro-2-of 1,1,3-tri-(fluoromethyl) propane; The fluoro-2-methylpropane of 1,1,1,3,3-five; The fluoro-2-of 1,1,3,3-tetra-(fluoromethyl) propane; The fluoro-2-of 1,1,1,3-tetra-(fluoromethyl) propane; Fluoro tetramethylene; 1,1-bis-fluoro tetramethylene; 1,2-bis-fluoro tetramethylene; 1,3-bis-fluoro tetramethylene; 1,1,2-tri-fluoro tetramethylene; 1,1,3-tri-fluoro tetramethylene; 1,2,3-tri-fluoro tetramethylene; 1,1,2,2-tetra-fluoro tetramethylene; 1,1,3,3-tetra-fluoro tetramethylene; 1,1,2,2,3-five fluoro tetramethylene; 1,1,2,3,3-five fluoro tetramethylene; 1,1,2,2,3,3-hexafluoro-tetramethylene; 1,1,2,2,3,4-hexafluoro-tetramethylene; 1,1,2,3,3,4-hexafluoro-tetramethylene; 1,1,2,2,3,3,4-seven fluoro tetramethylene and their mixture.

In certain embodiments, unsaturated hydrofluoroalkane can also be used.

In another embodiment, the solvent be applicable to comprises at least one oxygenatedchemicals, comprises C ₁-C ₂₂alcohol, ketone, ether, carboxylicesters and their mixture.

Alcohol comprises, but be not limited to: methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 2-methyl-2-propanol, 2-methyl isophthalic acid-propyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol, 3-methyl-2-butanols, tertiary amyl alcohol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, 4-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 2,3-dimethyl-2-butanols, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanols, 1-heptanol, 2-enanthol, 3-enanthol, 2-methyl-2-hexanol, 2-methyl-3-hexanol, 5-methyl isophthalic acid-hexanol, 5-methyl-2-hexanol, 2,2-dimethyl-3-amylalcohol, 2,3-dimethyl-3-amylalcohol, 2,4-dimethyl-3-amylalcohol, 4,4-dimethyl-2-amylalcohol, 3-ethyl-3-amylalcohol, 1-octanol, sec-n-octyl alcohol, 3-octanol, 4-methyl-3-enanthol, 6-methyl-2-enanthol, 2-ethyl-1-hexanol, 2-propyl group-1-amylalcohol, 2,4,4-trimethylammonium-1-amylalcohol and their mixture.

Ketone is including, but not limited to acetone, 2-butanone, 2 pentanone, propione, 3-methyl-2-butanone, methyl-n-butyl ketone, 3-hexanone, 2-methyl-propione, 3-methyl-2 pentanone, 4-methyl-2 pentanone, 2-heptanone, 3-heptanone, dipropyl ketone, 2-methyl-3-hexanone, 5 methy 12 hexanone, 2,4-dimethyl-propione, 4,4-dimethyl-2-pentanones, methyln-hexyl ketone, 3-octanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone and their mixture.

Ether is including, but not limited to methyl ether, tetrahydrofuran (THF), butyl methyl ether, sec-butyl methyl ether, t-butyl methyl ether, butyl ethyl ether, isopropyl ether, tert pentyl methyl ether, t-butyl ethyl ether, 2,2,5,5-tetramethyl-tetrahydrofuran (THF) and their mixture.

Acid is including, but not limited to acetic acid, propionic acid, butyric acid, isopropylformic acid, valeric acid, isovaleric acid, caproic acid, 2,2-acid dimethyls, 2 Ethylbutanoic acid, 2 methyl valeric acid, 3 methylvaleric acid, 4-methylvaleric acid, enanthic acid, 2 methyl caproic acid, sad, 2 ethyl hexanoic acid, valproic acid and their mixture.

Ester comprises, but be not limited to: methyl acetate, ethyl formate, ethyl acetate, isopropyl formate, methyl propionate, butyl formate, ethyl propionate, isopropyl acetate, propyl acetate, methyl-butyrate, methyl isobutyrate, butylacetate, sec-butyl acetate, tert.-butyl acetate, ethyl butyrate, ethyl isobutyrate, methyl trimethylacetate, methyl valerate, pentyl acetate, butyl propionate, propanoic acid tert-butyl ester, Ethylisovalerate, ethyl 2-methylbutyrate, tri-methyl ethyl acetate, Valeric acid ethylester, isopropyl butyrate, methyl caproate, pentyl acetate, propyl butyrate, butyl butyrate, hexyl acetate, isobutyl isobutyrate, ethyl hexanoate and their mixture.

In certain embodiments, prepare nano composite material by the following method, the method comprises: the solution A making to comprise solvent (this solvent comprises hydrocarbon) and at least one layered fillers with comprise solvent and contact with the elastomeric solution B of at least one; With in the product of contact from solution A and solution B except desolventizing to form nano composite material.

In foregoing embodiments, layered fillers can be the laminated clay with organic molecule process as above.

In still another embodiment, prepare nano composite material by the following method, the method comprises: make at least one elastomerics contact with at least one layered fillers in a solvent; With from product of contact except desolventizing to form nano composite material.

In another embodiment, prepare nano composite material by the following method, the method comprises: in the solvent mixture comprising two kinds of solvents, make at least one elastomerics contact with at least one layered fillers; With from product of contact, remove solvent mixture to form nano composite material.

In still another embodiment, prepare nano composite material by the following method, the method comprises: in the solvent mixture comprising at least two or more solvents, make at least one elastomerics contact with at least one layered fillers; With from product of contact, remove solvent mixture to form nano composite material.

In another embodiment, as prepared nano composite material by the following method, the method forms product of contact, is dissolved by least one elastomerics and then at least one layered fillers disperseed in the solvent mixture being included in solvent or comprising at least two kinds of solvents; With from product of contact, remove solvent mixture to form nano composite material.

In still another embodiment, prepare nano composite material by the following method, the method forms product of contact, the dispersion of at least one layered fillers is then dissolved by least one elastomerics in the solvent mixture being included in solvent or comprising at least two kinds of solvents; With from product of contact, remove solvent mixture to form nano composite material.

In the above-described embodiment, based on the gross weight of composition, the amount of solvent in the preparation of nanocomposite composition can be 30-99wt%, or 40-99wt%, or 50-99wt%, or 60-99wt%, or 70-99wt%, or 80-99wt%, or 90-99wt%, or 95-99wt%.

In addition, in certain embodiments, when preparing two or more solvents in the preparation at nanocomposite composition, often kind of solvent can account for 0.1-99.9 volume %, or 1-99 volume %, or 5-95 volume %, or 10-90 volume %, the cumulative volume of all solvents wherein existed is 100 volume %.

In still another embodiment, the invention provides for improvement of elastomeric bubble-tight method, it comprises makes at least one elastomerics, the layered fillers of at least one modification contacts to form nano composite material with solution; Wherein when measuring the nanocomposite composition of solidification described here or goods, the OTR oxygen transmission rate at 40 DEG C is 150mm.cc/ [m ². sky] or lower.

Or when measuring the nanocomposite composition of solidification described here, the OTR oxygen transmission rate at 40 DEG C is 150mm.cc/ [m ². sky] or lower; When measuring the nanocomposite composition of solidification described here, the OTR oxygen transmission rate at 40 DEG C is 140mm.cc/ [m ². sky] or lower; When measuring the nanocomposite composition of solidification described here, the OTR oxygen transmission rate at 40 DEG C is 130mm.cc/ [m ². sky] or lower; When measuring the nanocomposite composition of solidification described here, the OTR oxygen transmission rate at 40 DEG C is 120mm.cc/ [m ². sky] or lower; When measuring the nanocomposite composition of solidification described here, the OTR oxygen transmission rate at 40 DEG C is 110mm.cc/ [m ². sky] or lower; When measuring the nanocomposite composition of solidification described here, the OTR oxygen transmission rate at 40 DEG C is 100mm.cc/ [m ². sky] or lower; Or when measuring the nanocomposite composition of solidification described here, the OTR oxygen transmission rate at 40 DEG C is 90mm.cc/ [m ². sky] or lower.

Other component

The filler component that one or more are additional can also be comprised, as calcium carbonate, silicon-dioxide, clay and other can by or silicate, talcum, titanium dioxide and the carbon black that can not be stripped.Silicon-dioxide refer to any type or particle size by solution, pyrolysis or similar approach processing and there is the silicon-dioxide of surface-area or other silica derivative or silicic acid, comprise undressed precipitated silica, crystalline silica, colloid silica, pure aluminium silicate or Calucium Silicate powder, Fumed silica etc.

In one embodiment, additional filler is the carbon black of carbon black or modification, and these combination any.In another embodiment, additional filler can be the blend of carbon black and silicon-dioxide.

Be booster stage carbon black for the additional filler of goods as tire tread and sidewall, its amount is the 10-100phr of blend; In another embodiment, 30-80phr is more preferably; In still another embodiment, be 50-80phr.As described in RUBBER TECHNOLOGY (59-85), the carbon black of useful rank is N110-N990.More desirably, the embodiment of carbon black useful in such as tire tread is the N229 provided by ASTM (D3037, D1510 and D3765), N351, N339, N220, N234 and N110.The embodiment of carbon black useful in the sidewall of such as tire is N330, N351, N550, N650, N660 and N762.The carbon black being applicable to liner and other air retaining wall comprises N550, N660, N650, N762, N990 and Regal 85.

Additional filler can have any size and be generally such as about 0.0001 μm-about 100 μm.

In certain embodiments, composition described here and the goods be made up of those compositions can comprise at least one solidifying agent packaging.When using at this, at least one solidifying agent packaging refers to any material or method that can give the Cure of Rubber performance usually understood in industry.At least one solidifying agent packaging can comprise any following material.

One or more linking agents can also be used, as coupling agent, especially when silicon-dioxide exists with binding substances.Described coupling agent can be Bifunctionalized organosilane cross-linking agent." organosilane cross-linking agent " is any silane coupled filler well known by persons skilled in the art and/or activator of crosslinking and/or silane toughener; include but not limited to: vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, methyclyloxypropyl Trimethoxy silane, gamma-amino-propyl-triethoxysilicane (by Witco with A1100 commercial distribution), γ mercaptopropyitrimethoxy silane (A189 of Witco) etc., and their mixture.In one embodiment, two (3-triethoxysilylpropyltetrasulfide) tetrasulfide (with " Si69 " commercial distribution) is adopted.

Normally, blend polymer (be such as used for produce tire those) is crosslinked.As everyone knows, the physicals of vulcanizate compound, performance characteristics and weather resistance directly relevant with type to the crosslinked number (cross-linking density) formed during vulcanization reaction (see, such as Helt etc., The Post Vulcanization Stabilization for NR, RUBBER WORLD, 18-23 (1991)).Normally, can by adding solidifying agent molecule, such as sulphur, metal oxide, organometallic compound, radical initiator etc. then heat makes blend polymer be cross-linked.Specifically, following metal oxide is the Common Curing Agents that will play a role in the present invention: ZnO, CaO, MgO, Al ₂o ₃, CrO ₃, FeO, Fe ₂o ₃and NiO.These metal oxides can use individually or with corresponding fatty acid metal title complex (such as, Zinic stearas, calcium stearate etc.) combine use, or with the organism of described independent interpolation and lipid acid as stearic acid, and other optional solidifying agent such as sulphur or sulfocompound, alkyl peroxide compound, diamines or derivatives thereof (the DIAK product such as sold by DuPont) combine use.(also see, Formulation Design and Curing Characteristics of NBR Mixes for Seals, RUBBER WORLD 25-30 (1993)).This curing elastomeric can be accelerated and be generally used for elastomer blend sulfuration.

The acceleration of curing reaches by adding appropriate promotor (normally organic compound) in composition in the present invention.The mechanism of the accelerated cure of natural rubber comprises the interaction of solidifying agent, promotor, complexity between activator and polymkeric substance.Ideally, connected together by two polymer chains and improving in the effectively crosslinked formation of the bulk strength of polymeric matrix, all available solidifying agent are consumed.Much promotor is as known in the art and including, but not limited to following material: stearic acid, vulkacit D (DPG), tetramethyl-thiuram disulfide (TMTD), 4,4'-dithio morpholine (DTDM), tetrabutylthiuram disulfide (TBTD), 2-mercaptobenzothiazole disulphide (MBTS), the two sodothiol dihydrate of hexa-methylene-1,6-are (by Flexsys with DURALINK ^tMhTS commercial distribution), the blend of 2-(morpholinothio) benzothiazole (MBS or MOR), 90%MOR and 10%MBTS (MOR90), N tert butyl benzothiazole 2 sulfenamide (TBBS) and N-oxydiethylene thiocarbamyl-N-oxydiethylene sulphonamide (OTOS), 2 ethyl hexanoic acid zinc (ZEH) and " thiocarbamide ".

In one embodiment, nano composite material also comprises the solidifying agent being selected from sulphur, sulphur compounds, metal oxide, metal oxide complexes, lipid acid, superoxide, diamines and their mixture.

In other embodiments, because the existence of the multiple functionalized solidifying agent of at least one achieves desirable elastomerics pressuretightness.The embodiment of these multiple functionalized solidifying agent can by general formula Z-R ⁷-Z' describes, wherein R ⁷substituted or unsubstituted C ₁-C ₁₅alkyl, C ₂-C ₁₅thiazolinyl and C ₆-C ₁₂one of cyclic aromatic moiety; Z and Z' is identical or different and be the one in following group: thiosulfuric acid ester group, sulfydryl, aldehyde radical, carboxylic acid group, peroxide group, thiazolinyl or other similar a branch of or multi beam can be had reactive group as the group be cross-linked between the polymer molecule of unsaturated part or in molecule.So-called pair of thiosulfuric acid ester cpds is the example of the class polyfunctional compound be included in above-mentioned general formula.The limiting examples of these multiple functionalized solidifying agent is hexa-methylene two (Sulfothiorine) known in Rubber compounding techniques and hexa-methylene two (phenylacrolein) etc.These and other reagent be applicable to is at such as BLUE BOOK, MATERIALS, COMPOUNDING INGREDIENTS, disclose in MACHINERY AND SERVICES FOR RUBBER (Don.R.Smith edits, Lippincott & Petto Inc.2001).If existed, described multiple functionalized solidifying agent can with 0.1-8phr (in one embodiment) in nano composite material, and the amount of 0.2-5phr (in still another embodiment) exists.

Processing aid can also be comprised.Processing aid includes, but not limited to softening agent, tackifier, extender, chemical amendment, levelling agent and peptizer as mercaptan, oil and vulcanized vegetable oil, mineral oil, paraffin oil, polybutylene polymer, naphthenic oil, aromatic hydrocarbon oil, wax, resin, rosin, due to their low pour point, low emission etc. compared with paraffin or inorganic oil and for the synthetic fluid etc. of treated oil or auxiliary agent.

Described auxiliary agent exists with the amount of 1-70phr usually in one embodiment, exists in another embodiment, exist in another embodiment with the amount of 5-50phr with the amount of 3-60phr.

Some commercial embodiments of processing aid are SUNDEX ^tM(Sun Chemicals) (naphthenic process oils), PARAPOL ^tM(ExxonMobil Chemical Company) (number-average molecular weight is the polybutene processing oil of 800-3000) and FLEXON ^tM(ExxonMobil Chemical Company) (paraffin oil).In one embodiment of the invention, substantially there is not paraffin oil, naphthenic oil and aromatic hydrocarbon oil, namely wittingly they are not added in the composition for manufacturing air retaining wall, or, in replacement scheme, if existed, they only take the 0.2wt% at the most of the composition manufacturing air retaining wall.In another embodiment of the present composition, substantially there is not naphthenic oil and aromatic hydrocarbon oil.Their commercial embodiments comprises, such as FLEXON oil (they comprise some Aromatic moieties) and CALSOL oil (naphthenic oil).

Preferred softening agent also comprises poly-alpha olefins (PAO), high purity hydrocarbon fluid composition (HPFC) and III-th family basic material such as WO 2004/014998 and walks to those of the 24th page of the 1st line description for the 16th page the 14th.Especially preferred PAO comprises the oligopolymer of decene and the co-oligomer of decene and dodecylene.Preferred PAO can obtain from ExxonMobil Chemical Company (Houston, Texas) with trade(brand)name SuperSyn PAO.

In another embodiment, at least one plastomer may reside in blend of the present invention.Useful plastomer comprises unit and the 10-30wt%C of ethylene derivative ₃-C ₁₀alpha-olefin derived unit.In another embodiment, described plastomer comprises the unit that the unit of ethylene derivative and 10-30wt% are selected from the unit that 1-butylene, 1-hexene and 1-octene derive.In still another embodiment, described plastomer comprises the unit of ethylene derivative and the derivative unit of 10-30wt% octene.Described plastomer can have the melting index of 0.1-20dg/min, can have the melting index of 0.1-10dg/min in another embodiment.

In these embodiments, plastomer can be the unit of ethylene derivative the and more unit that derives of high alpha-olefin is as the multipolymer of the metallocene catalyst of propylene, 1-butylene, 1-hexene and 1-octene, and it comprises one or more enough these comonomer units to produce 0.860-0.900g/cm in one embodiment ³density.The molecular weight distribution (Mw/Mn) of desirable plastomer is 2-5 in one embodiment, is 2.2-4 in another embodiment.The example of these commercially available plastomeies is EXACT ^tMresin 4150 (multipolymer of ethene and 1-hexene), the unit that described 1-hexene derives accounts for the 18-22wt% of plastomer and has 0.895g/cm ³density and the MI (ExxonMobil Chemical Company, Houston, TX) of 3.5dg/min; And EXACT ^tMresin 8201 (multipolymer of ethene and 1-octene), the unit that described 1-octene derives accounts for the 26-30wt% of plastomer and has 0.882g/cm ³density and the MI (ExxonMobil Chemical Company, Houston, TX) of 1.0dg/min.

In one embodiment, the amount of plastomer in nano composite material is 2-20phr, is 10-15phr in another embodiment.

In one aspect of the method, nano composite material can also comprise treated oil or auxiliary agent.Described oil is selected from paraffin oil and polybutene processing oil and their mixture in one embodiment; Polybutene oil in another embodiment.Described treated oil amount is in one embodiment 2-20phr, and amount is in another embodiment 5-18phr.Rosinol amount in the compositions of the present invention can be 0.1-5phr in one embodiment, can be 0.2-2phr in another embodiment.Desirably, in one embodiment, what comprise that the oil at unsaturated position and processing aid account for the present composition is less than 2phr.

Nano composite material prepared in accordance with the present invention can also comprise other and be generally used for component in rubber size and additive, as non-discoloring in other of significant quantity and nondiscoloration processing aid, pigment, promotor, crosslinked and solidify material, antioxidant, antiozonidate.The promotor that one class is general comprises amine, diamines, guanidine, thiocarbamide, thiazole, thiuram, sulphenamide, sulfenamide, thiocarbamate, xanthate etc.Crosslinked and solidifying agent comprises sulphur, zinc oxide and lipid acid.Peroxide cure systems can also be used.Described component exists with the amount of 0.1-10phr with other solidifying agent is usual in the composition.

In another embodiment, nano composite material can also comprise additional rubber, it is selected from natural rubber, polyisoprene rubber, styrene butadiene rubbers (SBR), polybutadiene rubber, isoprene-butadiene rubber (IBR), styrene isoprene butadiene rubber (SIBR) (SIBR), ethylene-propylene rubber, Ethylene-Propylene-Diene rubber (EPDM), polysulphide, paracril, propylene oxide polymer, poly-(isobutylene-co-p-methylstyrene), halogenation gathers (isobutylene-co-p-methylstyrene), poly-(isobutylene-co-cyclopentadiene), halogenation gathers (isobutylene-co-cyclopentadiene) and their mixture.In another embodiment, composition also comprises 5-30phr natural rubber.

In certain embodiments, the useful formula for performance evaluation is as follows:

Carbon black N660 can obtain from such as Cabot Corp. (Billerica, MA).Stearic acid (solidifying agent) can obtain from such as C.K.Witco Corp. (Taft, LA), and Kadox911 (activator) can obtain from C.P.Hall (Chicago, IL).MBTS (2-mercaptobenzothiazole disulphide) can obtain from R.T.Vanderbilt (Norwalk, CT) or Elastochem (Chardon, OH).

Industrial applicability

Nano composite material of the present invention can be extruded, compression mold, blowing, injection-molded and be laminated into various moulded products, comprise fiber, film, nonwoven fabric from filaments, industrial part as trolley part, apparatus shell, the consumer's goods, packaging etc.

Specifically, described nano composite material is useful in goods are as truck tyre, passenger tyre, passenger car tire, motorcycle tyre, off-road tire, plane tyre etc.Described nano composite material can as the material of component manufacturing finished product or finished product.Described goods can be selected from air retaining wall, airtight film, film, nonwoven fabric from filaments (microbedding and/or multilayer), liner, the inner tube of a tyre, tyre surface, bladders and sidewall.

Embodiment

Table 1: embodiment 1-4

Cloisite ^tMna ⁺from Southern Clay Products, Inc., Gonzales, Texas obtain.Kunipia ^tMfrom Kunimine Industrial Co., Ltd., Japan obtains.SOMASIF ^tMmE-100 is from Co-Op Chemical Co., Ltd., and Japan obtains.

Methyl alcohol (500mL) to be added in reactor and to be heated to 60 DEG C.PIBA (NCS S00226) and HCl solution is added in this methyl alcohol.In this PIBA, its 33wt% is paraffin solvent.Before functionalized, the polymeric constituent of PIBA have by gel permeation chromatography be 1,000 number-average molecular weight.After stirring the mixture 3 hours, add na ⁺or filler also stirs this mixture 4 hours again.Then by solution collection in flask.Then by filling settlement to the bottom of flask to produce residual filler.Decantation goes out top transparent solution and is discarded.In residual filler, add methyl alcohol (300mL), described filler is deposited to again the bottom of flask.Decant goes out top transparent solution and is discarded again.Repeat this process twice.Last residual filler is washed with methyl alcohol (300mL).By solid air-dry then vacuum-drying a whole night at 100 DEG C of collecting.By product grinding and according to explanation measurement d spacing described here and in above-reported.

Table 2: embodiment 5-7

^*mooney viscosity is measured according to ASTM D 1646.

^*the isobutylene p-methylstyrene (can from ExxonMobil Chemical Company, Houston, TX obtain) of BIMS-bromination

BIMS 1 is dissolved in 500mL hexanaphthene in advance.This solution is transferred in reactor.The layered fillers of modification is added in this solution.Stir the mixture at 60 DEG C 3 hours.Evaporating solvent and under vacuo desciccate a whole night to produce dry product.36 grams of these desciccates are enclosed in the Branbender under 150 DEG C and 60rpm ^tMin mixing tank.After 1 minute, add 20 grams of carbon blacks and mix 7 minutes.All carbon black stocks are enclosed in the Branbender under 45 DEG C and 40rpm ^tMin mixing tank.After 1 minute, add conventional solidifying agent (stearic acid: 0.33 gram, Kadox 911:0.33 gram, MBTS:0.33 gram) and mix 3 minutes to produce compounding sample.Then this compounding sample ground, suppress and solidify and be used for carrying out perviousness measurement according to explanation described here and in above-reported.

Table 3: embodiment 8-11

Embodiment #	D spacing (dust)	Rate of permeation (mm.cc/m ². sky, 40 DEG C)
			Embodiment 8	86.14，15.64	--
Embodiment 9	--	102.84，103.97
			Embodiment 10	>88，14.43	--
Embodiment 11	--	95.65，95.70

Embodiment 8: PIBA (NCS S00226,5.0 grams) is added in methyl alcohol (200mL).In this solution, add HCl solution (concentration: 12M, volume: 1mL) and stir the mixture 2 hours.Then, will na ⁺(3.4 grams) to add in this solution and stir 3 hours at 80 DEG C.64 grams of BIMS 2 in 700mL hexane are added in this solution.After this mixture of stirring 2 hours, collect product and evaporating solvent.At 90 DEG C, it is dry further until the weight of sample keeps constant under vacuo.

Embodiment 9: 36 grams of desciccates (embodiment 8) are enclosed in the Branbender under 150 DEG C and 60rpm ^tMin mixing tank.After 1 minute, add 20 grams of carbon blacks and mix 7 minutes.Then this carbon black stock is enclosed in the Branbender under 45 DEG C and 40rpm ^tMin mixing tank.After 1 minute, add conventional solidifying agent (stearic acid: 0.33 gram, Kadox911:0.33 gram, MBTS:0.33 gram) and mix 3 minutes to produce compounding sample.Then by the grinding of this compounding sample and compacting be used for carrying out perviousness measurement according to explanation described here and in above-reported.

Embodiment 10: PIBA (NCS S00226,5.0 grams) is added in methyl alcohol (200mL) to produce solution.HCl solution (concentration: 12M, volume: 1mL) is added and stirred solution 2 hours in this solution.Then, add na ⁺(3.4 grams) also stir 3 hours at 80 DEG C.64 grams of BIMS 2 in 700mL hexane are added in this solution.After stirring the mixture 2 hours, product is poured in ethanol (800mL).Then use ethanol (200mL) washed product and repeat.At 90 DEG C, it is dry until the weight of sample keeps constant under vacuo.

Embodiment 11: 36 grams of desciccates (embodiment 10) are enclosed in the Branbender under 150 DEG C and 60rpm ^tMin mixing tank.After 1 minute, add 20 grams of carbon blacks and mix 7 minutes.This carbon black stock is enclosed in the Branbender under 45 DEG C and 40rpm ^tMin mixing tank.After 1 minute, add conventional solidifying agent (stearic acid: 0.33 gram, Kadox 911:0.33 gram, MBTS:0.33 gram) and mix 3 minutes to produce compounding sample.Then by the grinding of this compounding sample and compacting be used for carrying out perviousness measurement according to explanation described here and in above-reported.

Table 4: embodiment 12-13

At 70 DEG C, the unmodified clay of table 4 is loaded the reactor containing 180mL water and stirs the mixture 2 hours.In same period, half an hour the PIBA in tetrahydrofuran (THF) (THF) (70mL) is mixed with HCl solution by shake.In this solution, add two (octadecyl) ammonium of bromination dimethyl and within 1 hour, mixed by shake.Prepared solution to be added in reactor and to stir the mixture at 70 DEG C 6 hours.Then be added on BIMS 1 solution in hexanaphthene (500mL) and mix 12 hours.This solution is poured in Virahol (1.5L), then under vacuo 90 DEG C by dry 48 hours of this product to produce dry product.36 grams of desciccates (embodiment 10) are enclosed in the Branbender under 150 DEG C and 60rpm ^tMin mixing tank.After 1 minute, add 20 grams of carbon blacks and mix 7 minutes.Then this carbon black stock is enclosed in the Branbender under 45 DEG C and 40rpm ^tMin mixing tank.After 1 minute, add conventional solidifying agent (stearic acid: 0.33 gram, Kadox 911:0.33 gram, MBTS:0.33 gram) and mix 3 minutes to produce compounding sample.Then by the grinding of this compounding sample and compacting be used for carrying out perviousness measurement according to explanation described here and in above-reported.

The all patents quoted herein and patent application, testing sequence (as ASTM method) and other file are consistent with the present invention and for reference for allowing the degree of all authorities of this introducing is fully introduced in this publication.

When multiple lower limit and multiple upper limit are listed at this, should be considered from arbitrary lower limit to the scope of arbitrary upper limit.

Although the present invention has described exemplary embodiment in detail, be to be understood that other amendments various not departing from spirit and scope of the invention are apparent and easy to reach for a person skilled in the art.Therefore, do not wish the restriction of the embodiment that the claim appended by this is listed and explanation here, and think that claim comprises all features belonging to patent novelty of the present invention, comprise all features that those skilled in the art of the invention think their equivalent.

Claims

1. the preparation method of the layered fillers of modification, the layered fillers of this modification comprises at least one layered fillers and at least one properties-correcting agent, and described properties-correcting agent comprises at least one polymer chain E, and it is C that described polymer chain E comprises (a) carbon chain lengths ₄₀-C ₅₀₀end-functionalization poly-(iso-butylene) and the functionalized group of (b) ammonium, the method comprises:

Providing package contains with the solution of at least one layered fillers of at least one modifying agent to form product of contact;

Heat described solution;

Wash described product of contact; With

By described product of contact dry air and/or vacuum-drying.

2. the preparation method of the layered fillers of the modification of claim 1, the functionalized group of wherein said ammonium comprises ammonium salt, quaternary ammonium salt or tertiary amine salt, and described ammonium salt comprises at least one salt.

3. the preparation method of the layered fillers of the modification of claim 1, wherein said at least one laminated clay comprises at least one silicate.

4. the preparation method of the layered fillers of the modification of claim 1, wherein said at least one polymer chain E does not comprise the unit of propylene derived.

5. the preparation method of the layered fillers of the modification of claim 1, it is 35 dusts or larger layer that the layered fillers of wherein said modification comprises two or more d spacing.

6. the preparation method of the layered fillers of the modification of claim 1, wherein said solution comprise at least one layered fillers or at least one properties-correcting agent or they both, and before formation product of contact, this solution to be heated.

7. nanocomposite composition, comprises:

Elastic composition; With

The layered fillers of modification prepared by method according to claim 1.

8. the preparation method of the nanocomposite composition of claim 7, the method comprises solution blending.

9. the method for claim 8, wherein said solution blending comprises allows described elastic composition contact to form nanocomposite composition with the layered fillers of modification in the solution; With this nanocomposite composition is dry.

10. the method for claim 9, the solution A that wherein said solution blending comprises the layered fillers making to comprise modification contacts to form nanocomposite composition with the solution B comprising elastic composition.

The method of 11. claims 10, wherein said solution B comprises hydrocarbon solvent.

12. goods comprising nanocomposite composition, described nanocomposite composition comprises:

Elastic composition;

At least one solidifying agent is packed; With

The layered fillers of modification prepared by method according to claim 1.